Ruthenium-based metathesis catalysts, precursors for their preparation and their use

Patent metadata

Field	Value
Publication number	US-11577232-B2
Application number	US-202117562321-A
Country	US
Kind code	B2
Filing date	Dec 27, 2021
Priority date	Oct 29, 2012
Publication date	Feb 14, 2023
Grant date	Feb 14, 2023

Abstract

The invention is directed to ruthenium-based metathesis catalysts of the Grubbs-Hoveyda type. The new 2-aryloxy-substituted ruthenium catalysts described herein reveal rapid initiation behavior. Further, the corresponding styrene-based precursor compounds are disclosed. The catalysts are prepared in a cross-metathesis reaction starting from styrene-based precursors which can be prepared in a cost-effective manner.The new Grubbs-Hoveyda type catalysts are suitable to catalyze ring-closing metathesis (RCM), cross metathesis (CM) and ring-opening metathesis polymerization (ROMP). Low catalyst loadings are necessary to convert a wide range of substrates including more complex and critical substrates via metathesis reactions at low to moderate temperatures in high yields within short reaction times.

First claim

The invention claimed is:

1. A method for preparing
a ruthenium catalyst of formula (II)

comprising reacting a compound of formula (I)

wherein
a, b, c and d are, independently from each other, selected from hydrogen, straight chain or branched alkyl groups including C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylthio, C 1 -C 10 -silyloxy, C 1 -C 10 -alkylamino, optionally substituted C 6 -C 14 -aryl, optionally substituted C 6 -C 14 -aryloxy, optionally substituted C 6 -C 14 -heteroaryl or electron-withdrawing groups (EWG);
R 1 is hydrogen, straight chain or branched C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylthio, C 1 -C 10 -silyloxy, C 1 -C 10 -alkylamino, C 1 -C 10 -dialkylamino, C 6 -C 14 -aryl, C 6 -C 14 -aryloxy, C 6 -C 14 -heterocyclic or electron-withdrawing groups (EWG);
R 2 is hydrogen, straight chain or branched C 1 -C 10 -alkyl groups with a Ru-starting compound having the formula (V):

in a cross metathesis reaction,
wherein
L is a phosphine ligand selected from the group of tri-iso-propyl-phosphine, tricyclohexylphosphine (PCy 3 ), tricyclopentylphosphine, cyclohexylphobane, 2,2,4-trimethylpentylphobane or isobutyl-phobane or a NHC ligand selected from the group of 1,3-bis-(2,4,6-trimethylphenyl)-imidazolidine-2-ylidene (“SIMes”), 1,3-bis-(2,6-di-isopropylphenyl)-imidazolidine-2-ylidene (“SIPr”) or 1,3-bis-(2,6-di-isopropylphenyl)-imidazoline-2-ylidene (“IPr”) and
L′ is substituted or unsubstituted pyridine ligand;
X is an anionic ligand selected from the group of halogen anions (Cl − , Br − , I − ).

2. The method for preparing the catalysts according to claim 1 , wherein
L is a NHC ligand selected from the group of 1,3-bis-(2,4,6-trimethylphenyl)-imidazolidine-2-ylidene (“SIMes”), 1,3-bis-(2,6-di-isopropylphenyl)-imidazolidine-2-ylidene (“SIPr”) or 1,3-bis-(2,6-di-isopropylphenyl)-imidazoline-2-ylidene (“IPr”),
L′ is pyridine,
X is Cl − .

3. The method for preparing the catalyst according to claim 1 , wherein the electron-withdrawing groups are halogen atoms, trifluormethyl (—CF 3 ), nitro (—NO 2 ), sulfinyl (—SO—), sulfonyl (—SO 2 —), formyl (—CHO), C 1 -C 10 -carbonyl, C 1 -C 10 -carboxyl, C 1 -C 10 -alkylamido, C 1 -C 10 -aminocarbonyl, nitrile (—CN) or C 1 -C 10 -sulfonamide.

4. The method for preparing the catalysts according to claim 1 , wherein L is a N-heterocyclic carbene (NHC) ligand.

5. The method for preparing the catalysts according to claim 1 , wherein L is a N-heterocyclic carbene ligand having the formula (III) or (IV)

wherein
R 3 is selected from the group of 2,4,6-trimethylphenyl, 2,6-di-isopropyl-phenyl, 3,5-di-tert.-butylphenyl, 2-methylphenyl and combinations thereof.

6. The method for preparing the catalysts according to claim 1 , wherein
L is a NHC ligand selected from the group of 1,3-bis-(2,4,6-trimethylphenyl)-imidazolidine-2-ylidene (“SIMes”), 1,3-bis-(2,6-di-isopropylphenyl)-imidazolidine-2-ylidene (“SIPr”) or 1,3-bis-(2,6-di-isopropylphenyl)-imidazoline-2-ylidene (“IPr”);
X is Cl − ;
a, b, c and d each are hydrogen;
R 1 is hydrogen, dimethylamino (NMe 2 ), nitro (NO 2 ) or chlorine (Cl).

7. The method for preparing the catalysts according to claim 1 , wherein L is a phosphine ligand selected from the group of tri-isopropylphosphine, tricyclohexylphosphine (PCy 3 ), tricyclopentylphosphine and phospha-bicycloalkane compounds selected from the group of 9-cyclohexyl-9-phospha-bicyclo-[3.3.1]-nonane (“cyclohexylphobane”), 9-(2,2,4-trimethylpentyl)-9-phospha-bicyclo-[3.3.1]-nonane (“2,2,4-trimethylpentyl phobane”) and 9-isobutyl-9-phospha-bicyclo-[3.3.1]-nonane (“isobutylphobane”).

8. The method for preparing the catalysts according to claim 1 , the catalyst is a catalyst of formula (IIa)

9. The method for preparing the catalysts according to claim 1 , the catalyst is a catalyst of formula (IId)

10. The method for preparing the catalysts according to claim 1 , the catalyst is a catalyst of formula (IIe)

11. The method for preparing the catalysts according to claim 1 , the catalyst is a catalyst of formula (IIh)

Assignees

• Umicore Ag & Co Kg

Inventors

• Plenio Herbert
• Kos Pavlo
• Savka Roman

Classifications

• B01J2231/543

  alkene metathesis · CPC title

• C07F15/0046

  Ruthenium compounds · CPC title

• B01J2531/821

  Ruthenium · CPC title

• C07C43/29

  containing halogen · CPC title

• B01J31/2273

  with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes · CPC title